Manufacture and use of azo dyestuffs



Patented Oct. 5, 1943 lT ED STATES rm, ENT- orjrrca 1 use or no 7 "nYEs'rUFFs nmyoimies flfpim'and Edmund Stanley, Spondon, 'near Derby, England, "assignors 10 Gelane'se florporatiomof America, a corporation of Delaware 12 claims. (01. 260 152) This invention'-i.-'e1ates to the production of new azo dyes "in substance 'or on a substratum and more particularly to the cbltifiraitioh of textile materials made of or containing cellulose acetate or other cellulose ester "or ether, especially by the azoic'p'roc'ess.

According to the invention valuable water-insoluble azo dyes are obtained by coupling a tetrazotised aromatic di-primary-amine with an ary'lamide of a "3-hydro'xy-2-carboxy di -phenyl'ene oxide. In addition to the hydroxy and the carbox'yl'ic arylainide groups other substituents may be present in the diphenylene oxide radicle, providing that any additionalsubstituents are'not such 'as to induce water-soliibility-in the-a'zo dye or to condition coupling with a diazo com onent in any position other than the 4-p0sition of the diphenyle'ne oxide 'r'adicle. The (ii-primaryamine-also must be free tram-groups which would induce water solubility in the azo dye.

"The a'zo dyes may be formedin substancebut the invention is, as mentioned :above, more-particularly concerned with the "formation of the dyes on textile or other materials, especially cellulose ester or ether materials, by the-'az'oic process. Valuable dark shadesof goodfastnessproperties may thusbeiproduced.

The use of a di-primary-am-ine as diazo component r-generally leads to "darker and richer shades than those obtainable with a mono-amine. In particular, by suitable choice of components "rich dark brown shades maybe produced. v Advantageously, a 4:4'-diaminoazobenzene or other 4:4'diamino azo compound is used as the The arylamide ofthe 3-hydroxy-2-carboxy-di- 'ph'enylene oxide which is used "as coupling component'may be derivedir'om any desired aromatic amine whether of the "benzene or naphthalene or other'series. A'sexa'mples ofsuitableamin'esmention may be made of anilino, 'ortho- "or-paratoliiidine, xylidines "and the halogen, nitrobr alk'o'xy substitution products of these amines. Again aorfi-naplithylamine or substitution lp'roducts thereof may befused. 'aryl'amide which hasbe'en round to give especially good results in the process of the invention is the 225'.- di-methoxy-anilide of 3-hydroxy-2-car'boxy-diphenylene oxide.

As examples of specific combinations giving valuable dark brown shades mentionmaybe made of thedyestuffs derived from the last mentioned coupling component and tetrazotised '4:4"-'diamino-azo-benzene or 4 4" -diamino-'2-chlor-5' methoxy-Z'-methyl-azo-benzene.

in effecting the colouration of-cellulose este or ether textile materials by "formation of the dyes of the invention on the fibre materials may be treated as described in British Specification No. 404,363 and U. S. Patent No. 1,844,350, first with an alkali free dispersion of the coupling component and then with the diazo solution, or the diazo-component may first be applied from a dispersion, diazotised on the materials and thereafter developed or if desired both diazo component and coupling component may be applied from dispersion to the materialsand diazotisation and coupling effected thereon. In the latter case the amine and coupling component may be applied togetheror separately as may be desired or convenient. Advantageously. however, instead of using an alkali-free dispersion of a coupling component a small amount of alkali may be present. In either case whether the coupling component is applied from an alkaline medium or from an alkali free dispersion it is in practice found particularly advantageous to apply both diazo and coupling components from a single bath. Where both components {are applied to the materials prior to the diazotisation the latter may be effected by treating the materials with'a'nitrite solution acidified with a suitable 'acid,'for example acetic acid. The presence of acid during the coupling is best avoided and to this end in order to complete the coupling after 'diazotisation the materials may besubjected to an alkaline treatment, .particularlyto the action of a weakly alkaline bath such as a very dilute sodium carbonate solution.

As dispersing agents and/or protective colloids there may be used in the dye-bath Turkey redoil and/or a sulphonated or sulphated fatty alcohol such as oleyl sulphate. Formaldehyde or glucose, preferably the latter, may beadded as astabiliser. Furthermore glucose is of value when alkali is present in that it 'reduces the risk of saponific'ation-of and consequent damage to cellulose acetate and other cellulose ester materials.

'As mentioned above, valuable dark shades may be produced by forming the =d yes on cellulose ester #or ether textiles. Still darker s'hades maiy be obtained by forming the dyes on dark coloured cellulose ester or ether materials produced by shaping and setting a solution of a cellulose ester or ether containing a dyestufi as described, for example in U. S. Patent No. 2,128,338, and U. S. applications S. Nos. 221,362, filed July 26, 1938, and 237,469, filed October 28, 1938. a

The invention also includes the formation of the dyes in substance, in which form they may be used in printing pastes, as pigments or as .additions to artificial silk spinning solution. 'By shaping and setting the last mentioned solutions coloured filaments, foils, films and like products can be obtained. For example'the dyes of the invention may be incorporated in asolution of cellulose acetate in a volatile organic solvent and the product dry spun to form coloured threads.

Alternatively, one or both of the components necessary for the formation 'of the dye may be incorporated in the spinning solution and development of the dyestuff in the formed materials subsequently effected.

The invention is of particular value in connection with the colouration of cellulose acetate materials. It may, however, also be applied to the colouration of other. esters of cellulose, for example, cellulose formate, cellulose propionate, cellulose butyrate or, cellulose acetate-butyrate or cellulose ethers, for example, ethyl or benzyl cellulose. Further the new dyes may be formed on other types of artificial or natural fibres, for example, cotton or regenerated cellulose.

The invention is illustrated by the following examples: r

' EXAMPLE 1 To dye a rz'ch brown shade on cellulose acetate yarn For 1 kilo of cellulose acetate yarn the dyebath is set as follows:

Soft water litres 40 Dispersing agent grams 40 Glucose Q. "do' 60 2z5" dimethoxyanilide of 3-hydroxy-2-carboxy-diphenylene oxide grams 30 Caustic soda flakes do 20 4:4 diamino-2-chlor-5 methoxy-2'methylazobenzene gi'a1ns The dispersing agent may be Turkey red oil or of the sulphated fatty alcohol type. The base,

. 4 4 -diamino-2-chlor-5 -metl1oxy-2 -methylazo- Glacial acetic acid cc. per litre 8 Sodium nitrite" gms. per litre 4 the Volume ratio of liquor to yarn being 30-40zl. After 30 minutes the yarn is again rinsed and turned in a bath set with Soap gms. per litre 1 Sodium carbonate do 0.5

at a temperature of 40 C. and gradually raised to 65 C. till coupling is'complete.

The yarn is finally rinsed, finished and dried.

EXAMPLE 2 To prepare a dark brown dyestufi in substance 106 gms. of 4:4 diaminoazobenzene are tetrazotised in known manner with 70 gms. of sodium nitrite and 300 cos. of concentrated hydrochloric acid.

The diazo solution is run with stirring into a solution containing 363 gms. of 2':5'dimethoxyanilide of 3-hydroxy-2-carboxy-diphenylene oxide dissolved in the minimum quantity of caustic soda solution and maintained alkaline throughout the coupling by the addition of sodium carbonate solution. The end point is adjusted in the usual manner by the addition of either diazo solution or coupling component and the dyestuif well washed and dried.

, It may then be suitably dispersed by grinding or othermeans, incorporated in a spinning solution of cellulose acetate and spun to give brown coloured yams of very good fastness properties.

Having described our invention, what we desire to secure by Letters Patent 1's:

1. Process for the production of polyazo dyestuffs, which comprises coupling a tetrazotized aromatic di-primary-amino azo compound of the general formula (NH2(R) .N=N.(R)NH2, wherein R and R," are aromatic radicles selected from the group consisting of radicles containing a single benzene nucleus and radicles containing a single naphthalene nucleus and wherein both the amino groups are in the para position to the azo group, with the 25-di methoxy anilide of 3-hydroxy-2-carboxy-diphenylene oxide.

2. Process for the production of azo'dyes, which comprises coupling a tetrazotized 4.4'-diaminoazobenzene with the 25'-dimethoxy anilide of 3-hydroxy-2-carboxy-diphenylene oxide.

3. Process for the production of azo dyes, which comprisescoupling a tetrazotized 4.4-diamino-2- chlor-5-methoxy-2'-methylazobenbene with the 25'-dimethoxy anilide of 3-hydroxy-2-carboxydiphenylene oxide.

4. Process for the production of azo dyes, which comprises coupling tetrazotized 4.4-diaminoazobenzene with the 25-dimethoxy anilide of 3-hydroxy-2-carboxy-diphenylene oxide.

5. An azo dye obtainable by coupling a tetrazotized .aromatic di-primary-aminoazo compound of the general formula NH2(R).N=N.(R")NH2, wherein R and R" are aromatic radicles selected from the group consisting of radicles containing a single benzene nucleus and radicles containing a single naphthalene nucleus and wherein both the amino groups are in the para position to the azo group, with the 25'-dimethoxy-anilide of 3 hydroxy-Z-carboxy-diphenylene oxide.

6. An azo dye obtainable by coupling a tetrazotized 4.l'-diaminoazobenzene with the 2'5- dimethoxy anilide of 3-hydroxy-2-carboxy-diphenylene oxide.

7. An azo dye obtainable by coupling a tetrazotized 4.4 diamino 2 chlor 5- methoxy-2- methylazobenzene with the 25'-dimethoxy anilide of 3-hydroxy-2-carboxy-diphenylene oxide. 8. An azo dye obtainable by coupling tetrazo- .tized 4.4'diaminoazobenzene with the 25-dimethoxy anilide of 3-hydroxy-2-carboxy-diphenylene oxide.

.9. Cellulose acetate textile materials colored with an azo dye obtainable by coupling a tetrazotized aromatic di-primary-aminoazo compound of the general formula NI-Iz(R).N=N.(R")NH2, wherein R and R," are aromatic radicles selected from the group consisting of radicles containing with an azo dye obtainable by coupling a. tetrazotized 4.4'-diamino-2-chlor-5'-methoXy-2'-methylazobenzene with the 2'5'-dimethoxy anilide of 3-hydroxy-2-carboxy-diphenylene oxide.

12. Cellulose acetate textile materials colored with an azo dye obtainable by coupling tetrazotized 4.4'-diamino-2-ch1or-5'-methoxy-2'-methylazobenzene with the 2'5'-dimethoxy 'anilide of 3-hydroxy-2-carboxy-diphenylene oxide.

HENRY CHARLES OLPIN. EDMUND STANLEY. 

